Naphtholactam dyestuffs

ABSTRACT

A dyestuff of the formula ##STR1## in which R represents alkyl, alkenyl, cycloalkyl, aralkyl, aryl or, preferably, hydrogen, R 1  represents alkyl, alkenyl, cycloalkyl, aralkyl, a heterocyclic structure or, preferably, aryl, X represents --COOH, --COO.sup.⊖ cation.sup.⊕, a modified carboxyl group, the radical --SO 2  --T or a heterocyclic radical, T being alkyl, alkenyl or aryl, and M represents hydrogen or a cation and A and B can carry non-ionic substituents and/or a --COOH group. 
     The new dyestuffs dye polyester fibers in fast yellow and orange shades.

This is a continuation of application Ser. No. 797,275, filed May 16,1977, now abandoned.

The invention relates to naphtholactam dyestuffs of the general formula(I) ##STR2## in which R represents alkyl, alkenyl, cycloalkyl, aralkyl,aryl or, preferably, hydrogen, R₁ represents alkyl, alkenyl, cycloalkyl,aralkyl, a heterocyclic structure or, preferably, aryl, X represents--COOH, --COO.sup.⊖ cation.sup.⊕, a modified carboxyl group, the radical--SO₂ --T or a heterocyclic radical, T being alkyl, alkenyl or aryl, andM represents hydrogen or a cation and A and B can carry non-ionicsubstituents and/or a --COOH group.

The new dyestuffs of the formula (I) can be manufactured by variousprocesses.

A particularly advantageous process consists in subjecting anaphtholactam compound of the formula (II) ##STR3## to a condensationreaction, in the presence of an acid condensing agent, preferablyphosphorus oxychloride, with a compound of the formula ##STR4## whichcontains an active methylene group, and optionally subsequentlysulphonating, brominating, chlorinating, nitrating and/or saponifyingthe resulting condensation product; in the formulae R, X, A, B and R₁have the meaning indicated above.

Another of these processes is characterized in that a compound of theformula ##STR5## in which W represents a C₁ -C₄ -alkyl radical,preferably methyl or ethyl, An represents an anion and R, A and B havethe meaning indicated above, is subjected to a condensation reactionwith a compound of the formula (III), W-SH and H-An being split off.

A further particularly advantageous manufacturing process ischaracterized in that the hydrazides of the formula

    NC--CH.sub.2 --CO--NH--NH--CO--R.sub.1                     (V)

in which R₁ has the same meaning as above, are employed in place of thecompound of the formula (III) and, if desired, the resulting product issulphonated, brominated, chlorinated, nitrated and/or saponified.

Suitable groups R₁ are C₁ -C₅ -alkyl or aryl, such as phenyl, toluyl,methoxyphenyl, ethoxyphenyl, chlorophenyl, nitrophenyl or carboxy-C₁ -C₃-alkylphenyl.

Examples of non-ionic substituents on the rings A and B are alkyl,alkoxy, halogen, nitro, alkylmercapto, alkylsulphonyl, arylsulphonyl,acylamino, cyano, chlorocarbonyl, carboxamide, carboxylic acid ester,carboxylic acid hydrazide and sulphonamide, and alkyl is to beunderstood, in particular, as alkyl with 1 to 4 carbon atoms, such asmethyl, ethyl, propyl, isopropyl and n-butyl, alkoxy groups are to beunderstood, in particular, as those with 1 to 4 carbon atoms, such asmethoxy, ethoxy, n-propoxy, n-butoxy and isopropoxy, halogen radicalsare to be understood as, in particular, chlorine and bromine, inaddition to fluorine, alkylmercapto and alkylsulphonyl are to beunderstood, in particular, as those which have 1 to 4 carbon atoms inthe alkyl radical, such as methylmercapto, β-hydroxyethylmercapto,isopropylmercapto or n-butylmercapto or methylsulphonyl,β-hydroxyethylsulphonyl, isopropylsulphonyl or n-butylsulphonyl,arylsulphonyl is to be understood, in particular, as phenylsulphonyl,aralkylsulphonyl is to be understood as, preferably, benzylsulphonyl,acylamino is to be understood, in particular, as C₁ -C₄-alkylcarbonylamino, such as acetylamino, and C₁ -C₄-alkylsulphonylamino, such as methylsulphonylamino, and carboxamide andsulphonamide radicals are to be understood, in particular, ascarboxamide or sulphonamide radicals which are substituted by one or twoalkyl radicals which contain 1 to 4 carbon atoms, such as methyl, ethylor n-butyl.

Dyestuffs which, in the 4-position, contain an optionally modifiedcarboxylic acid group, such as --COOH, --CN, --COCl, --CO--Q' or,preferably --CO--OR'₁, in which Q' is the radical of an amine H--Q' andR'₁ is optionally substituted alkyl, alkenyl, cycloalkyl, aralkyl oraryl or a heterocyclic radical, are particularly preferred. Thesedyestuffs can contain a second substituent, such as, for example, ahalogen atom, especially a chlorine atom or bromine atom, in the5-position.

Preferred dyestuffs are those of the formula ##STR6## in which X and R₁have the same meaning as above, W₁ denotes hydrogen, chlorine, bromine,alkyl, alkoxy, nitro or arylmercapto, W₂ denotes hydrogen or chlorine,W₃ denotes hydrogen, chlorine, bromine, alkyl, alkoxy, nitro, acylamino,alkylsulphonylamino, arylsulphonylamino, alkylmercapto, arylmercapto,arylsulphonyl, alkylsulphonyl, optionally N-substituted sulphonamide,alkanoyl or aroyl, W₄ denotes hydrogen, chlorine, bromine, alkoxy,arylmercapto or the COOH group and its modified radicals, W₃ and W₄conjointly denote a radical of the formula ##STR7## and W₅ denoteshydrogen, chlorine or alkoxy.

W₁ is, for example, methyl, ethyl, methoxy, ethoxy, phenylmercapto orphenylmercapto which is substituted by chlorine, methyl, methoxy,phenyl, phenoxy or methoxycarbonyl.

Radicals to be mentioned for W₃ are the same radicals as for W₁ as wellas naphthylmercapto, acetylaminophenylmercapto, acetylamino,propionylamino, benzoylamino, benzoylamino which is substituted bychlorine, bromine, methyl or methoxy, methylsulphonylamino,ethylsulphonylamino, phenylsulphonylamino, tolylsulphonylamino,methylmercapto, ethylmercapto, β-hydroxyethylmercapto, methylsulphonyl,ethylsulphonyl, phenylsulphonyl, tolylsulphonyl, chlorophenylsulphonyl,acetyl, propionyl, butyryl, benzoyl, benzoyl which is substituted bymethyl, methoxy, chlorine or bromine, sulphamoyl, N-methyl-, N-ethyl-,N-butyl-, N-phenyl-, N-chlorophenyl-, N-methylphenyl-, N-methoxyphenyl-,N-trifluoromethylphenyl-, N-methyl-N-phenyl-, N,N-dimethyl-,N,N-diethyl-, N,N-dipropyl- or N,N-dibutyl-sulphamoyl,pyrrolidinosulphonyl, piperidinosulphonyl or morpholinosulphonyl. Theradicals of the formulae NHCONH₂,NHCONHCH₃ or NHCONHC₆ H₅ are alsopossible.

Radicals W₄ are, in addition to hydrogen and chlorine, the alkoxy andarylmercapto radicals mentioned for W₁ and, above all, modifiedcarboxylic acid radicals.

Alkoxy radicals W₅ are, for example, methoxy or ethoxy.

Further valuable dyestuffs are those of the formula ##STR8## in which R,R₁ and X have the same meaning as above, Y₁ represents hydrogen,chlorine, bromine, lower alkyl, lower alkoxy, nitro, loweralkylmercapto, lower alkylsulphonyl or acylamino and Y represents --CN,--COCl, --CO-Q' or, preferably, --CO--OR'₁, in which Q' and R' have thesame meaning as above.

Dyestuffs of the formula VII in which X is --CO--OR₁ ", --CO--Q, --SO₂--T, a heterocyclic structure or, preferably, --CN and R"₁ denotesoptionally substituted alkenyl, cycloalkyl, aralkyl, aryl or,preferably, alkyl, T is alkyl, alkenyl or, preferably, aryl and Q is theradical of an amine of the formula Q--H, Y₁ is chlorine, bromine orhydrogen and Y represents --CO--Q' or --CO--OR'₁, in which Q' and R'₁have the same meaning as above, are preferred.

In the carboxamide groups --CO--Q and --CO--Q', the radicals Q and Q',of the amines QH and Q'H, independently of one another denotemethylamino, ethylamino, dimethylamino, diethylamino, dipropylamino,di-n-butylamino, N-methyl-N-butylamino, N-(2-hydroxy-, 2-chloro-,2-methoxy-, 2-bromo- or 2-cyanoethyl)-amino, N,N-di-(2-hydroxy-,2-chloro-, 2-methoxy- or 2-cyano-ethyl)-amino,N-2-cyanoethyl-N-ethylamino, N-2-cyanoethyl-N-2-hydroxyethylamino,N-2-lower alkoxy (for example C₁ -C₄ -alkoxy)-N-lower alkyl (for exampleC₁ -C₄ -alkyl-, especially methyl)-amino,N-methoxyethyl-N-cyanoethylamino, N-methyl-N-ethylamino,N-2-methylthioethylamino, N-2-methylsulphonylethylamino,γ-methoxypropylamino, γ-cyanopropylamino, γ-carboxypropylamino,γ-sulphopropylamino, radicals of the formula (lower alkyl)₂ N(CH₂)₁₋₄-NH--, such as dimethylamino-ethylamino or dibutylamino-ethylamino,radicals of the formula (N-morpholinyl-, N-pyrrolidinyl- orN-piperidinyl-)-(CH₂)₁₋₄ -NH--, N-hydroxyethyl-N-cyclohexylamino,3-hydroxy-1,1-dimethylpropylamino, benzylamino, o-, m- orp-nitrobenzylamino, o-, m- or p-methylbenzylamino, o-, m- orp-methoxybenzylamino, phenylethylamino, cyclohexylamino,methylcyclohexylamino, 2,2,5-trimethylcyclohexylamino,dicyclohexylamino, tetramethylenesulphonyl-3-amino, N-pyrrolidinyl,N-piperidinyl, N-morpholinyl, N-4-sulphopiperidinyl (N-thiomorpholinyl),##STR9## N-(N'-lower alkyl (for example methyl))-piperazinyl,N-(N'-lower alkylcarbonyl (for example acetyl))-piperazinyl,N-(N'-hydroxyethyl)-piperazinyl, phenylamino, o-, p- orm-chlorophenylamino, 3,6-dichlorophenylamino, o-, m- orp-bromophenylamino, o- or p-fluorophenylamino,m-trifluoromethylphenylamino, m- or p-nitrophenylamino, o-, m- or p-methylphenylamino, o-, m- or p-lower alkoxyphenylamino, such as o-, m-or p-methoxyphenylamino, m- or p-carboxyphenylamino, m- orp-carboxamidophenylamino, m- or p-acetamidophenylamino, p- orm-aminosulphonylphenylamino,m-bis-(hydroxyethylamino)-sulphonylphenylamino,methylsulphonylphenylamino, p-(2-hydroxyethyl)-sulphonylphenylamino,N-cyclohexyl-N-phenylamino, N-methyl-N-phenylamino,N-phenyl-N-2-hydroxyethyl-amino, N-phenyl-N-2-cyanoethyl-amino,N-p-chlorophenyl-N-2-hydroxyethylamino, p-phenoxyphenylamino,p-(p'-chlorophenoxy)-phenylamino, p'-methylphenoxyphenylamino,m-chloro-o-phenoxyphenylamino, p-benzylphenylamino andp-acetamidophenylamino and p-propionylamidophenylamino, amino radicalsof the formula ##STR10## in which Z' represents the members necessary tocomplete a 5-membered or 6-membered ring, such as, for example,thiazolyl-2-amino, benzthiazolyl-2-amino, benzoxazolyl-2-amino,1,3,4-triazolyl-2-amino, 1-thia-3,4-diazolyl-2-amino andbenzimidazolyl-2-amino and their methoxy, ethoxy, phenyl, chlorine,bromine, methyl, ethyl, carbomethoxy and carboethoxy derivatives, α- andβ-tetrahydrofurfurylamino, 2-furfurylamino, N-α- and-β-tetrahydrofurfuryl-N-methylamino, thiophenyl-2-amino andpyridyl-3-amino, and the amino radicals derived from sulphanilic acidand taurine.

Preferably, the amines HQ and HQ' are so chosen that the radicals Q andQ' represent the groups of the formulae NHR'₂ and NR'₂ R'₃, in which R'₂and R'₃ are optionally substituted aralkyl radicals and, if R'₂ is anoptionally substituted lower alkyl radical, R'₃ can also be anoptionally substituted aryl radical and, if R'₂ is a hydrogen atom, R'₃can be an optionally substituted alkyl radical, an optionallysubstituted aralkyl radical or an optionally substituted aryl radical.

Radicals R are, in addition to hydrogen, in particular alkyl with 1 to 8carbon atoms, hydroxyalkyl with 2 or 3 carbon atoms, alkoxyalkyl with 3to 8 carbon atoms, β-chloroethyl, β-cyanoethyl, alkoxycarbonylethyl with1 to 4 carbon atoms in the alkoxy, carbamoylethyl, N-monosubstituted orN,N-disubstituted alkylcarbamoylethyl with 1 to 4 carbon atoms in thealkyl, cyclohexyl, benzyl, phenylethyl or phenyl and also alkenyl.Aliphatic groups, as well as benzyl and phenethyl and, above all, ahydrogen atom are preferred.

Examples which may be mentioned individually are: propyl, butyl, hexyl,β-ethylhexyl, β-hydroxyethyl or β-hydroxypropyl, methoxyethyl,ethoxyethyl, methoxypropyl, ethoxypropyl, butoxypropyl, amyloxypropyl,methoxycarbonylethyl, ethoxycarbonylethyl, allyl or butoxycarbonylethyland, preferably, methyl, ethyl or β-cyanoethyl.

Individual meanings which are possible for the groups R'₁, R'₂, R'₃ andR"₁ are, for example, the following: C₁ -C₁₈ -alkyl groups, which areoptionally substituted by C₁ -C₄ -alkoxy, hydroxyl, chlorine, bromine,cyano, carboxyl, carb-C₁ -C₄ -alkoxy, sulpho, carboxamide or acetoxy;examples which may be mentioned are methyl, butyl, propyl, ethyl, octyl,β-cyanoethyl, β-chloroethyl, β-hydroxyethyl, β-hydroxypropyl,β-hydroxy-γ-chloropropyl, β-carboxyethyl, β-carbomethoxyethyl,β-carboethoxyethyl or β-carbobutoxyethyl, β-carboxamidoethyl andβ-acetoxyethyl; as well as cycloaliphatic groups, such as cyclopentyl,methylcyclohexyl, trimethylcyclohexyl and, preferably, cyclohexyl; orphenyl, benzyl or phenethyl which are optionally substituted by C₁ -C₄-alkyl, such as methyl, lower alkoxy, such as methoxy, or halogen, suchas chlorine.

When it is used in connection with definitions, such as alkyl, alkoxy,carbalkoxy and the like, the term "lower" denotes that the alkylradicals which occur in the radical contain not more than 4 carbonatoms.

Examples of non-ionic substituents on the rings A and B are alkyl,alkoxy, halogen, nitro, alkylmercapto, alkylsulphonyl, arylsulphonyl,acylamino, cyano, carboxamide and sulphonamide, and alkyl is to beunderstood, in particular, as alkyl with 1 to 4 carbon atoms, such asmethyl, ethyl, isopropyl and n-butyl, alkoxy groups are to beunderstood, in particular, as those with 1 to 4 carbon atoms, such asmethoxy, ethoxy, n-propoxy, n-butoxy and isopropoxy, halogen radicalsare to be understood as, in particular, chlorine and bromine, inaddition to fluorine, alkylmercapto and alkylsulphonyl are to beunderstood, in particular, as those which have 1 to 4 carbon atoms inthe alkyl radical, such as methylmercapto, β-hydroxy-ethylmercapto,isopropylmercapto or n-butylmercapto or methylsulphonyl,β-hydroxy-ethylsulphonyl, isopropylsulphonyl or n-butylsulphonyl,arylsulphonyl is to be understood, in particular, as phenylsulphonyl,aralkylsulphonyl is to be understood as, preferably, benzylsulphonyl,acylamino is to be understood as, in particular, C₁ -C₄-alkylcarbonylamino, such as acetylamino, and C₁ -C₄-alkylsulphonylamino, such as methylsulphonylamino, and carboxamide andsulphonamide radicals are to be understood, in particular, ascarboxamide or sulphonamide radicals which are substituted by one or twoalkyl radicals which contain 1 to 4 carbon atoms, such as methyl, ethylor n-butyl.

Groups which confer solubility in water are, above all, sulphonic acidgroups and groups which have positively charged (quaternary) nitrogenatoms. It is true that free carboxyl groups (--COOH) are as a ruleincluded amongst the groups conferring solubility in water, but these asa rule effect solubility in water only in the form of their salts, forexample the alkali metal salts, so that their exclusion merelyrepresents a preferred embodiment.

Possible cations M are those of inorganic or organic bases, possibleinorganic cations being, in particular, alkali metal cations, such asNa, K and Li, and ammonium, and possible organic cations being, forexample, pyridinium, alkyl-ammonium and dialkyl-ammonium, in which thealkyl groups preferably have 1 to 4 carbon atoms, as well as cations ofbasic dyestuffs. Monosulphonated dyestuffs are preferred.

The reaction of the naphtholactam of the formula (II) with the compoundsof the formula (III) which contain an active methylene group is carriedout in the presence of an acid condensing agent, such as phosphorusoxybromide, phosphorus trichloride, phosphorus tribromide, phosphoruspentachloride, thionyl chloride , phosgene (in an autoclave) or mixturesof phosphorus oxychloride and phosphorus pentoxide, but especially inthe presence of phosphorus oxychloride.

The reaction is advantageously carried out with heating, for example attemperatures of 50° to 200° C., but preferably in a range from 60° to130° C. It is appropriately carried out in an inert organic solvent suchas benzene, toluene, xylene, chlorobenzene, dichlorobenzene,nitrobenzene, ethylene chloride, carbon tetrachloride or chloroform.

The condensation reaction of compound IV and V is carried out underalkaline reaction conditions, appropriately in an organic solvent, suchas methanol, ethanol, butanol, ethylene glycol monomethyl ether,dimethylformamide, pyridine or chlorobenzene, in the presence of acondensing agent having an alkaline reaction, such as triethylamine,potassium carbonate, sodium hydroxide or magnesium oxide, at elevatedtemperature, appropriately at 40° to 160° C. and preferably at 60° to100° C.

The starting materials of the formula (III) are accessible by a knownroute by reacting a naphtholactam compound of the formula (V) withdiphosphorus pentasulphide to give the corresponding thione compound andreacting the latter with quaternising agents R-An, preferably dimethylsulphate.

The optional subsequent sulphonation of compounds of the formula I whichare free from sulphonic acid groups is appropriately carried out byreacting the compounds with customary sulphonating agents, preferablyoleum containing 5 to 60% of SO₃, one to two sulpho groups beingintroduced by this means. The reaction is appropriately carried out attemperatures between 5° and 50° C. by methods which are in themselvesknown.

The optional nitration is carried out in the customary manner using amixture of nitric acid and sulphuric acid and halogenation is carriedout by means of the action of elementary bromine or chlorine.

A further route to the dyestuffs of the formula I consists in carryingout the condensation reaction with halogen-containing condensing agents,such as, in particular, phosphorus oxychloride, so that a --CO-halogenogroup, especially a chlorocarbonyl group, is formed in the 4-position ofthe naphtholactam and this group is subsequently reacted with alcohols,phenols, amines or mercaptans to give the corresponding esters, amidesor thio-esters.

Alcohols and phenols which are suitable for the reaction are, forexample, methanol, ethanol, n-propanol, i-propanol, butanol,sec.-butanol, iso-butanol, 1,2-dihydroxybutane, 2,5-dihydroxyhexane,3-methyl-1,5-dihydroxypentane, 2-ethylhexanol, 2,2-dimethylpentanol,2,2,4-trimethylpentanol, dodecyl alcohol, octadecyl alcohol, benzylalcohol, cyclohexanol, allyl alcohol, methallyl alcohol, cinnamylalcohol, lauryl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurylalcohol, diethylene glycol monomethyl ether or diethylene glycolmonoacetate, triethylene glycol monobutyl ether, ethylene glycol,1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,neopentylglycol, 2,2-diethylpropane-1,3-diol,2-ethyl-2-butylpropane-1,3-diol, 2-ethyl-2-propylpropane-1,3-diol,2,2,4-trimethylhexane-1,6-diol, 2-ethyl-2-methylpropane-1,3-diol,1,10-decanediol, diethylene glycol, triethylene glycol,β,β'-thiodiethanol, 1,1-, 1,2-, 1,3- and 1,4-dimethylolcyclohexane and1,2-, 1,3- and 1,4-α,α'-xylene glycol.

Examples of amino alcohols, which give esters which are possible here,are 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol,2-amino-2-methylpropanol, 2-aminobutanol, 3-aminobutanol,3-amino-2-butanol, 3-amino-3-methyl-2-butanol, 2-methylaminoethanol,2-dimethylaminoethanol, 2-ethylaminoethanol, 2-diethylaminoethanol,3-methylaminopropanol, 3-dimethylaminopropanol, 3-ethylaminopropanol,3-dimethylaminopropanol, 1-methylamino-2-propanol,1-dimethylamino-2-propanol, 1-ethylamino-2-propanol,1-diethylamino-2-propanol, 3-methylaminobutanol, 3-dimethylaminobutanol,3-ethylaminobutanol, 3-diethylaminobutanol, 3-methylamino-2-butanol,3-dimethylamino-2-butanol, 3-ethylamino-2-butanol,3-diethylamino-2-butanol, 2-(2-aminoethylamino)-ethanol,N-(2-hydroxyethyl)-piperidine, 2-aminocyclohexanol,2-methylaminocyclohexanol, 2-dimethylaminocyclohexanol,2-benzylaminoethanol and α-aminomethylbenzyl alcohol. Phenol and mono-and poly-alkylphenols, for example 2-, 3- or 4-methyl-, -ethyl-,-n-propyl-, -isopropyl-, -n-butyl-, -isobutyl-, -tert.-butyl-, -n- or-iso-pentyl-, -n- or -iso-dodecyl-, -n- or -iso-palmityl-, -n- or-iso-stearyl-, -ethane-, -propene-, -butene- and -ethine-phenol, 2,3-,2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethyl-, -diethyl- and -dipropylphenols,2,3,4-, 2,3,5-, 2,3,6-, 3,4,5- or 2,4,6-trimethyl-, -triethyl- and-tripropyl-phenols, 2,3,4,6-, 2,3,4,5- or 2,3,5,6-tetramethyl-,-tetraethyl- and -tetrapropyl-phenols and 2,3,4,5,6-pentamethylphenol,it also being possible for the abovementioned alkyl radicals to bemixed, for example 2,6-dimethyl-4-tert.-butylphenol; cycloalkylphenols,for example 2-, 3- or 4-cyclohexylphenol; substituted alkylphenols, forexample 4-chloromethyl-, 4-hydroxymethyl- and 3-trifluoromethyl-phenol;aralkylphenols, for example 2-, 3- or 4-benzylphenols; arylphenols, forexample 2-, 3- or 4-hydroxydiphenyl; alkylamino-, arylamino- andacylamino-phenols, for example 2-, 3- or 4-acetylamino-, 2-, 3- or4-benzoylamino-, 2-, 3- or 4-methacroylamino- andN-methyl-N-formyl-4-aminophenol; halogenophenols, for example 2-, 3- or4-chloro- or -bromo-phenol, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichloro(bromo)-phenol, 2-methyl-5-chloro-, 2-methyl-6-chloro,3-methyl-4-chloro-, 5-methyl-2-chloro-, 2-methyl-4-chloro- or2-methyl-3-chloro-phenol and3,5,3',5'-tetrachloro-2,2'-dihydroxydiphenyl; nitrophenols, for example2-, 3-or 4-nitrophenol, 2-methyl-5-nitro-, 4-methyl-2-nitro,3-methyl-4-nitro-, 4-methyl-3-nitro- and 3,5-dimethyl-4-nitro-phenol;hydroxyphenylsulphonic acids and hydroxyphenylcarboxylic acids and theiresters and amides, for example 3- or 4-hydroxybenzoic acid or-benzenesulphonic acid, 2-, 3- or 4-hydroxybenzoic acid (or-benzenesulphonic acid) methyl ester, propyl ester, isobutyl phenylester, naphthyl ester and halogenophenyl esters,2-hydroxy-5-chlorobenzoic acid ester, 2-cyanato-3-methyl-benzoic acidesters, 2-, 3- or 4-hydroxybenzoic acid dimethylamide, diethylamide,morpholylamide or piperidylamide; alkoxy-, aryloxy- and acyloxy-phenols,for example 2-, 3- or 4-methoxy-, -ethoxy-, -propoxy-, -isopropoxy-,-butoxy-, -phenoxy-, -acetoxy- and -benzoxy-phenols,N,N-dialkylcarbamate and 4-allyl-2-methoxyphenol; acylphenols, forexample 2-, 3- or 4-acetyl-, -propionyl- and -benzoylphenol and4-acetyl-1,3-dihydroxybenzene; cyanophenols, for example 2-, 3- or4-cyanophenol; phenols with S-containing substituents, for example 2-,3-or 4-methylmercapto-, -ethylmercapto-, -propylmercapto-,-phenylmercapto-, -acetylmercapto- and -benzoylmercapto-phenols, 3- or4-mercaptophenols, 2,4-bismethylmercapto-3-methyl-phenol and ##STR11##polyhydric phenols, such as, for example, pyrocatechol, hydroquinone,resorcinol and the like; alkylated dihydroxyphenols, such as, forexample, 1,3-dihydroxy-4-methylbenzene or 1,2-dihydroxy-4-hexylbenzene;alkoxylated dihydroxyphenols, such as, for example,1,4-dihydroxy-3-hexoxybenzene; cycloaliphatic phenols, such as, forexample, p-cyclopentylphenol or p-cyclohexylphenol; halogenateddihydroxyphenols, such as, for example, 1,2-dihydroxy-4-chlorobenzene;trihydric phenols, such as, for example, phloroglucinol or pyrogallol;and polynuclear phenols, such as, for example,2,2-bis-(p-hydroxyphenyl)-propane, 4,4'-dihydroxydiphenyl,2,2'-dihydroxydiphenyl, 2,4'-dihydroxydiphenyl anddihydroxynaphthalenes, such as 2,6-dihydroxynaphthalene, can also beused. Dihydroxyarylsulphones, for examplebis-(p-hydroxyphenyl)-sulphone, 2,4'-dihydroxydiphenylsulphone,5'-chloro-2,4-dihydroxydiphenylsulphone,5'-chloro-2,4'-dihydroxydiphenylsulphone,3'-chloro-4,4'-dihydroxydiphenylsulphone andbis-(4-hydroxyphenyl)-biphenyldisulphone, can also be used.

Aromatic dihydroxy-ethers, for example p,p'-dihydroxydiphenyl ether,p,p'-dihydroxytriphenyl ether, the 4,3'-, 4,2'-, 3,3'-, 2,2'- and2,3'-dihydroxydiphenyl ethers and 4,4'-dihydroxy-2,5-dimethyldiphenylether, are also suitable, as are the addition products of equimolaramounts of ethylene oxide and mercaptans, and also n-butylmercaptan,phenylmercaptan, 2-, 3- or 4-chlorophenylmercaptan, 2,4- or2,5-dichlorophenylmercaptan, 2-, 3- or 4-methylphenylmercaptan, 2,4- or2,5-dimethylphenylmercaptan, 2-, 3- or 4-methoxyphenylmercaptan, 2,4- or2,5-dimethoxyphenylmercaptan, 2- or 4-nitrophenylmercaptan, 2- or4-carbomethoxyphenylmercaptan, 2-mercapto-benzthiazole,2-mercapto-6-chloro-benzthiazole, 2-mercapto-4-chloro-benzthiazole,2-mercapto-4-methyl-benzthiazole, 2-mercapto-6-methylbenzthiazole,2-mercapto-6-methoxy-benzthiazole, 2-mercapto-6-ethoxy-benzthiazole,2-mercapto-benzoxazole and 2-mercaptobenzimidazole.

Compounds H₂ N-NR₃ R₄ which can be employed, optionally in the form oftheir salts, such as hydrochlorides, hydrobromides, hydroiodides,nitrates, sulphates or acetates, are, for example, the followinghydrazines and hydrazides and cyclohexanone hydrazone: methylhydrazine,isopropylhydrazine, phenylhydrazine, 2-nitrophenylhydrazine,3-nitrophenylhydrazine, 4-nitrophenylhydrazine,2,4-dinitrophenylhydrazine, 2-chlorophenylhydrazine, N-aminopiperidine,N-aminopyrrolidine, N-aminomorpholine, N-aminocarbazole,N-aminotetrahydro(iso)quinoline, methanesulphonic acid hydrazide,ethanesulphonic acid hydrazide, isopropanesulphonic acid hydrazide,hexanesulphonic acid hydrazide, cyclohexanesulphonic acid hydrazide, C₁-C₅ -alkanoylhydrazides, such as acetylhydrazide, benzoylhydrazide,benzenesulphonic acid hydrazide, 2-, 3- or 4-toluenesulphonic acidhydrazide, 2-, 3- or 4-chloro-(bromo- or fluoro-)benzenesulphonic acidhydrazide, 2-, 3- or 4-hydroxybenzenesulphonic acid hydrazide, 2-, 3- or4-dimethylaminobenzenesulphonic acid hydrazide, 2-, 3- or4-nitrobenzenesulphonic acid hydrazide, 2-, 3- or4-methylmercapto-benzenesulphonic acid hydrazide, quinolinesulphonicacid hydrazides, carbazolesulphonic acid hydrazides,phenylpyrazolonesulphonic acid hydrazides and imidazolesulphonic acidhydrazides.

The naphtholactam compounds of the formula II which are employed asstarting materials are known. Examples which may be mentioned are:1,8-naphtholactam, 4-methoxy-1,8-naphtholactam,4-bromo-1,8-naphtholactam, 4-chloro-1,8-naphtholactam,2,4-dichloro-1,8-naphtholactam, 4-nitro-1,8-naphtholactam,4-methylsulphonyl-1,8-naphtholactam,4-morpholinosulphonyl-1,8-naphtholactam,4-methylmercapto-1,8-naphtholactam, 4-sulpho-1,8-naphtholactam and2-methyl-1,8-naphtholactam.

The naphtholactam compounds, employed as starting materials, which havesubstituents in the 4-position which are derived from a carboxyl groupare obtainable by reacting o-xylylene dicyanide with glyoxal in thepresence of a base (NaOH or KOH) and a solvent at temperatures below 50°C. (for example 0° to 40° C.) to give 1,4-dicyanonaphthalene andsubsequently either (a) saponifying the 1,4-dicyanonaphthalene in abasic or, preferably, acid medium to give the 1,4-dicarboxylic acid andeither converting the 1,4-naphthalene-dicarboxylic acid into afunctional derivative and then converting the latter, using a 10 to 50%excess of nitric acid, to the 8-nitro-1,4-naphthalene-dicarboxylic acidderivative and reducing this to the 8-amino derivative, or nitrating the1,4-naphthalenedicarboxylic acid direct and subsequently reducing thereaction product to the 8-amino-naphthalene-1,4-dicarboxylic acid, andthen converting the 8-amino derivative into the1,8-naphtholactam-4-carboxylic acid, or functional derivatives thereof,either by spontaneous cyclisation or by warming, or (b) nitrating the1,4-dicyanonaphthalene in the 8-position using a 10 to 50% excess ofnitric acid and subsequently reducing the nitro group to the 8-aminogroup, effecting naphtholactam cyclisation cyano group in the4-position, if this has not already been saponified during the reductionof the 8-nitro group, in a basic or acid medium, optionally via thestage of the 4-carboxamido-1,8-naphtholactam.

The naphtholactams which contain an organic group as the substituent Ron the lactam ring are obtained, for example, by alkylating thecorresponding naphtholactams which carry hydrogen on the nitrogen atomof the lactam ring (R=H) in a polar aprotic solvent, such asdimethylformamide or N-methylpyrrolidone, with a toluenesulphonic acidester of the formula ##STR12## in the presence of a strong base, such assodium hydroxide or potassium hydroxide. R has the same meaning asabove.

The dyestuffs of the formula I give brilliant, luminous yellow to reddyeings which usually fluoresce in UV light and have outstandingfastness properties in use, the dyestuffs which are free from groupsconferring solubility in water being especially valuable.

The new dyestuffs are preferably free from sulphonic acid groups and aresuitable for dyeing semi-synthetic and fully synthetic fibres, such asacrylic fibres or acrylonitrile fibres, polyacrylonitrile fibres andcopolymers of acrylonitrile and other vinyl compounds, such asacrylates, acrylamides, vinylpyridine, vinyl chloride or vinylidenechloride, copolymers of dicyanoethylene and vinyl acetate and alsoacrylonitrile block copolymers, fibres made of polyurethanes,polyolefines, such as base-modified, nickel-modified or unmodifiedpolypropylene, and cellulose triacetate and cellulose 21/2-acetate andespecially fibres made of polyamides, such as Nylon-6, Nylon-6,6 orNylon-12, and fibres made of aromatic polyesters, such as those ofterephthalic acid and ethylene glycol or 1,4-dimethylolcyclohexane andcopolymers of terephthalic acid and isophthalic acid and ethyleneglycol.

Dyeing of the said fibre materials with the dyestuffs, which preferablyare sparingly soluble in water, is preferably effected from an aqueousdispersion.

It is therefore appropriate finely to divide those dyestuffs which canbe used as disperse dyestuffs, by grinding with textile auxiliaries,such as, for example, dispersing agents and possibly grindingauxiliaries. Subsequent drying gives dyestuff formulations which consistof the textile auxiliary and the dyestuff.

Examples which may be mentioned of dispersing agents, of the non-ionicgroup, which can advantageously be used are: addition products of 8 molsof ethylene oxide with 1 mol of p-tert.-octylphenol, of 15 or 16 mols ofethylene oxide with castor oil and of 20 mols of ethylene oxide with thealcohol C₁₆ H₃₃ OH, addition products of ethylene oxide withdi-[α-phenylethyl]-phenols, polyethylene oxide tert.-dodecyl thioethers,polyamine polyglycol ethers or addition products of 15 or 30 mols ofethylene oxide with 1 mol of the amine C₁₂ H₂₅ NH₂ or C₁₈ H₃₇ NH₂.

Anionic dispersing agents which may be mentioned are: sulphuric acidesters of alcohols of the fatty series with 8 to 20 carbon atoms, of theethylene oxide adducts of the corresponding fatty acid amides, or ofalkylated phenols with 8 to 12 carbon atoms in the alkyl radical;sulphonic acid esters containing alkyl radicals with 8 to 20 carbonatoms; sulphation products of saturated fats and oils; phosphoric acidesters containing alkyl radicals with 8 to 20 carbon atoms; fatty acidsoaps and also alkylarylsulphonates, condensation products offormaldehyde and naphthalenesulphonic acid and ligninsulphonates.

Suitable cationic dispersing agents are quaternary ammonium compoundswhich contain alkyl or aralkyl radicals with 8 to 20 carbon atoms.

In addition to the dispersing agents, the dyestuff formulations can alsocontain organic solvents, especially solvents which boil above 100° C.and which preferably are miscible with water, such as mono- anddi-alkylglycol ethers, dioxane, dimethylformamide or dimethylacetamide,tetramethylenesulphone or dimethylsulphoxide. The dyestuff, thedispersing agent and the solvent can advantageously be ground together.

A dyestuff formulation of this type is manufactured, for example, bymixing 2 to 30, and preferably 5 to 20, percent by weight of thedispersing agent to a paste with 10 to 55 percent by weight, andpreferably approximately the two-fold to four-fold amount, of thedyestuff and about 10 to 20 parts of a glycol or of anotherwater-retaining agent. Subsequently, for example, the pH value isadjusted to about 9 with a dilute acid, preferably with sulphuric acidor acetic acid, and the mixture is then made up to 100% with water. Themixture is then ground to the necessary fineness, for example in a glassmill or another dispersing apparatus, and during this operation thegrinding temperature can be between 20° and 90° C.

The dyeing of the polyester fibres with the dyestuffs according to theinvention, which are sparingly soluble in water, from an aqueousdispersion is carried out by the processes customary for polyestermaterials. Polyesters of aromatic polycarboxylic acids with polyhydricalcohols are preferably dyed at temperatures of above 100° C. underpressure. However, dyeing can also be carried out at the boiling pointof the dye bath in the presence of colour-transfer agents, for examplephenylphenols, polychlorobenzene compounds or similar auxiliaries, orcan be effected by the thermosol process, that is to say padding withsubsequent hot after-treatment, for example thermofixing, at 180° to210° C.

Cellulose 21/2-acetate fibres are preferably dyed at temperatures of 80°to 85° C., whilst cellulose triacetate fibres are advantageously dyed atthe boiling point of the dye bath. The use of colour-transfer agents canbe dispensed with when dyeing cellulose 21/2-acetate fibres or polyamidefibres. Dyestuffs according to the invention can also be used forprinting the said materials by customary methods.

The dyeings obtained according to the present process can be subjectedto an after-treatment, for example by heating with an aqueous solutionof a non-ionic washing agent.

According to the present process it is also possible to apply theindicated compounds by printing, instead of by impregnating. For thispurpose, for example, a printing ink which contains the finely disperseddyestuffs in addition to the auxiliaries customary in printing, such aswetting agents and thickeners, is used.

Furthermore, for example, synthetic fibres, such as polyesters andpolyamides, can be dyed in organic solvent liquors, such as in a mixtureof perchloroethylene and dimethylformamide or in pure perchloroethylene.

Deep, luminous dyeings and prints with excellent fastness properties,especially fastness to light, thermofixing, sublimation, pleating, fluegas, cross-dyeing, drycleaning, ironing, rubbing, chlorine and wetprocessing, such as fastness to water, washing and perspiration, areobtained by the present process.

The new dyestuffs, which are insoluble in water, can also be used forspin-dyeing polyamides, polyesters and polyolefines. The polymer to bedyed is appropriately mixed, in the form of a powder, granules or chips,as a ready-to-use spinning solution or in the molten state with thedyestuff, which is introduced in the dry state or in the form of adispersion or solution in an optionally volatile solvent. Afterhomogeneous dispersion of the dyestuff in the solution or melt of thepolymer, the mixture is processed in a known manner by casting, pressingor extruding to fibres, yarns, monofilaments, films and the like.

The dyestuffs according to the invention are outstandingly suitable forcolouring oils or macromolecular materials, such as lacquers, films,sheets and mouldings, for example those made of cellulose esters, suchas cellulose 21/2-acetate and cellulose triacetate, polyvinyl compounds,such as polyvinyl chloride and polyvinyl acetate; polyurethanes,polystyrene, polyesters, polyamides and polycarbonates in bulk. Thedyestuffs which can be used for this application are, in particular, thecompounds of the formula I which are not in the form of a salt and alsothose which contain sulpho groups and are in the form of salts ofsuitable organic cations, such as, for example, those of alkylamineswhich solubilise fats or of basic dyestuffs.

The dyestuffs according to the invention possess high fastness to light,even in light dyeings and in combination with other disperse dyestuffs,high brilliance (fluorescence), high fastness to sublimation, a lowsensitivity to carriers in respect of the fastness to light and a highdepth of colour, coupled with a good reserve for other fibres, forexample wool fibres. They also have only a low sensitivity to changes inpH and are especially suitable for the high temperature process and thethermosol process as well as for permanent press finishing ("Koratron"process). They are also suitable for printing by all customaryprocesses, including, inter alia, for the printing of mixed fabrics.

They possess a high fastness to light, good stability to heat and goodsolubility, even in the case of bulk dyeings (especially polyesterspinning compositions). Coupled with a high fastness to sublimation,they display no migration on the surface when the fibres are subjectedto heat treatments (for example on texturing) and display good fastnessto rubbing.

The sulphonated representatives of the dyestuffs according to theinvention are in the main used for dyeing wool and synthetic polyamidesand, for this purpose, aqueous solutions which contain textileauxiliaries, such as, for example, levelling agents, are used.

In the examples which follow, parts denote parts by weight, unlessotherwise stated, percentages denote percentages by weight and thetemperatures are given in degrees Centigrade.

Preparation of the starting materials

(a) 15.6 parts by weight of o-xylylene dicyanide and 8.5 parts by weightof glyoxal hydrate (trimer) (3C₂ H₂ O₂.2H₂ O) containing 80% of glyoxalto be liberated are stirred into 200 parts by volume of methanol. 11.2parts by weight of powdered potassium hydroxide are added in portions tothe reactionmixture, at 15°, whilst stirring and under nitrogen.

After the potassium hydroxide has been added, the reaction mixture isstirred for a further 15 hours at room temperature and under nitrogen.The slightly brown-coloured reaction mixture is then freed from methanolin vacuo and diluted with 500 parts by volume of water. The crude1,4-dicyanonaphthalene which has precipitated is filtered off and washedwith water until neutral. 11 parts by weight (61.8% of theory) of1,4-dicyanonaphthalene are obtained in the form of slightlybrown-coloured small needles with a melting point of 175° to 185° C.

After recrystallising once from alcohol with the aid of 5 parts byweight of active charcoal, 5.5 parts by weight of the compound ##STR13##are obtained in the form of beautiful needles with a melting point of204° to 205° C.

(b) 46.4 g of technical grade naphthalene-1,4-dicarboxylic acid (93%pure) are introduced at a temperature of 20° to 25° into a stirred flaskwhich contains 480 g of 93% strength sulphuric acid, whilst stirring.The resulting thick suspension is cooled to 0° and a mixture consistingof 22 g of 63% strength nitric acid and 22 g of 93% strength sulphuricacid is allowed to run in dropwise in the course of 30 minutes at 0° to2°, with external cooling. The mixture is then stirred for a further 5hours at 0° to 5° and is then poured onto 1 kg of fine ice. The productwhich has precipitated is filtered off using a suction filter and iswashed with water until neutral, after which the resulting product ofthe formula ##STR14## is dried in vacuo at 70°. Yield 45 g.

For purification, 45 g of the crude product are heated briefly to theboil with 225 ml of glacial acetic acid, the mixture is then allowed tocool and the product which has precipitated is filtered off at roomtemperature. This gives the nitro compound in the form of a pale greypowder which dissolves completely in water when sodium carbonate isadded. Melting point 252°.

(c) 52 parts of 8-nitro-naphthalene-1,4-dicarboxylic acid are dissolvedin 700 parts of absolute ethyl alcohol and the solution is boiled underreflux for 12 hours whilst continuously passing in hydrogen chloridegas. The resulting solution is evaporated in vacuo. The4-ethoxycarbonyl-8-nitro-naphthalene-1-carboxylic acid of the formula##STR15## which is obtained in this way, melts at 178° to 180°.

If the monoester is hydrogenated, the 4-ethoxycarbonyl-1,8-naphtholactamdescribed above is obtained and this confirms that the esterification ofthe carboxylic acid group has taken place in the 4-position.

(d) 130 parts of 8-nitro-naphthalene-1,4-dicarboxylic acid are dissolvedin 500 parts of dimethylformamide, 40 parts of sodium hydroxide areadded and after stirring for 30 minutes 170 parts by volume of diethylsulphate are added all at once. The temperature then rises to 90°. Themixture is stirred for 2 hours, paying no attention to the temperature,a small amount of impurities is then filtered off from the solution andthe filtrate is discharged into 2,500 parts by volume of a 10% strengthsodium chloride solution and 50 parts by volume of a 30% strength sodiumhydroxide solution. After stirring briefly, diethyl8-nitro-naphthalene-1,4-dicarboxylate with a melting point of 107° to109° is filtered off, washed and dried.

(e) 32 parts of diethyl 8-nitro-naphthalene-1,4-dicarboxylate arestirred into 200 parts of glacial acetic acid and, after adding 20 partsof iron powder, the mixture is boiled under reflux for 6 hours. Forworking up, the mixture is filtered hot, the filtrate is diluted with anequal volume of water and the 4-ethoxycarbonyl-1,8-naphtholactam whichis thus precipitated is filtered off, washed until neutral and dried.The product of the formula ##STR16## which is obtained in good yield,melts at 216° to 218°. Analysis gave the following values

    ______________________________________                                                     C        H        N                                              ______________________________________                                        calculated:    69.7       4.6      5.8                                        found:         69.3       4.5      5.6                                        ______________________________________                                    

(f) 29 parts of dimethyl 8-nitro-naphthalene-1,4-dicarboxylate (whichcan be prepared analogously to Example 5 using dimethyl sulphate) aredissolved in 500 parts of ethyl acetate and hydrogenated with Raneynickel. 4-Methoxycarbonyl-8-amino-1-naphtholactam precipitates outvirtually completely. After the hydrogenation has ended, the mixture isfiltered and the residue is extracted with methylglycol. Evaporation ofthe extraction solution gives the ester of the formula ##STR17## with amelting point of 264° to 266°. Analysis gave the following values:

    ______________________________________                                                     C        H        N                                              ______________________________________                                        calculated:    68.72      3.99     6.17                                       found:         68.5       4.0      5.9                                        ______________________________________                                    

(g) 24 parts of 4-ethoxycarbonyl-8-amino-1-naphtholactam are boiled in180 parts of water and 20 parts of a 30% strength sodium hydroxidesolution for one hour under reflux, during which time everything goesinto solution. This solution is filtered with charcoal whilst still hotand the filtrate is acidified. The 8-amino-1-naphtholactam-4-carboxylicacid which has precipitated is filtered off after cooling and washedwith water and dried.

EXAMPLE 1

A mixture consisting of 4.80 g of 5-ethoxycarbonylnaphtholactam, 4.10 gof the hydrazide of the formula ##STR18## (obtained by reactingcyanoacetic acid hydrazide with benzoyl chloride in aqueous-alkalinesolution) and 30 ml of chlorobenzene is stirred at a temperature of 100°and a mixture of 6.30 ml of phosphorus oxychloride and 6 ml ofchlorobenzene is allowed to run in dropwise in the course of about 30minutes, after which the mixture is stirred for a further 90 minutes atthe same temperature. It is then allowed to cool and the precipitatewhich has formed is filtered off and washed with chlorobenzene and thenwith petroleum ether. The material on the filter is now suspended in 50ml of isopropanol, the suspension is heated to 60° and 40 ml of pyridineare added. After cooling, the dyestuff which has precipitated isisolated by filtration and washed with isopropanol and then with water,after which the resulting dyestuff of the formula ##STR19## is dried invacuo at 70°. For purification, the dyestuff is recrystallised from 7parts of dimethylsulphoxide.

When applied as a disperse dyestuff from an aqueous liquor at 130°, thedyestuff dyes fabric made of polyethylene terephthalate brilliantorange. The dyeings have good fastness to sublimation and light.

If, with an otherwise identical procedure, equivalent amounts of thenaphtholactam compounds listed under I in the table which follows areused in place of 5-ethoxycarbonylnaphtholactam and the hydrazides ofcolumn II are used in place of the hydrazide indicated above, thedyestuffs of column III, which have similar properties, are obtained.

    __________________________________________________________________________                                                               IV                 I                                                          Shade              Naphtholactam     II                   III                 on                 compound          Hydrazide compound   Dyestuffs           PET                __________________________________________________________________________        ##STR20##                                                                                    ##STR21##                                                                                          ##STR22##          orange             2                                                                                 ##STR23##     "                                                                                                   ##STR24##          "                  3                                                                                 ##STR25##     "                                                                                                   ##STR26##          "                  4                                                                                 ##STR27##     "                                                                                                   ##STR28##          "                  5                                                                                 ##STR29##     "                                                                                                   ##STR30##          "                  6                                                                                 ##STR31##                                                                                    ##STR32##                                                                                          ##STR33##          "                  7                                                                                 ##STR34##     "                                                                                                   ##STR35##          "                  8                                                                                 ##STR36##     "                                                                                                   ##STR37##          "                  9                                                                                 ##STR38##     "                                                                                                   ##STR39##          "                  10                                                                                ##STR40##     "                                                                                                   ##STR41##          "                  11                                                                                ##STR42##                                                                                    ##STR43##                                                                                          ##STR44##          "                  12                                                                                ##STR45##     "                                                                                                   ##STR46##          "                  13                                                                                ##STR47##                                                                                    ##STR48##                                                                                          ##STR49##          "                  14                                                                                ##STR50##     "                                                                                                   ##STR51##          "                  15                                                                                ##STR52##     "                                                                                                   ##STR53##          "                  16                                                                                ##STR54##                                                                                    ##STR55##                                                                                          ##STR56##          yellow             17   "                                                                                           ##STR57##                                                                                          ##STR58##          "                  18   "                                                                                           ##STR59##                                                                                          ##STR60##          "                  19   "                                                                                           ##STR61##                                                                                          ##STR62##          "                  20   "            NCCH.sub.2CONHNHOCCH.sub.3                                                                          ##STR63##          "                  21   "            NCCH.sub.2CONHNHOCC.sub.2 H.sub.5                                                                   ##STR64##          "                  22   "                                                                                           ##STR65##                                                                                          ##STR66##          "                  23   "                                                                                           ##STR67##                                                                                          ##STR68##          "                  24                                                                                ##STR69##     "                                                                                                   ##STR70##          "                  25   "                                                                                           ##STR71##                                                                                          ##STR72##          "                  26   "                                                                                           ##STR73##                                                                                          ##STR74##          "                  27                                                                                ##STR75##                                                                                    ##STR76##                                                                                          ##STR77##          "                  28   "                                                                                           ##STR78##                                                                                          ##STR79##          "                  29                                                                                ##STR80##                                                                                    ##STR81##                                                                                          ##STR82##          "                  30                                                                                ##STR83##     "                                                                                                   ##STR84##          "                  __________________________________________________________________________

EXAMPLE 2

2 g of the dyestuff obtained according to Example 1 are dispersed in4,000 g of water. 12 g of the sodium salt of o-phenylphenol, as aswelling agent, and 12 g of diammonium phosphate are added to thisdispersion and 100 g of a yarn made of polyethylene glycol terephthalateare dyed for 11/2 hours at 95° to 98°. The dyeing is rinsed andafter-treated with aqueous sodium hydroxide solution and a dispersingagent.

This gives an orange dyeing which is fast to washing, light andsublimation.

If, in the above example, the 100 g of polyethylene glycol terephthalateyarn are replaced by 100 g of cellulose triacetate fabric, dyeing iscarried out under the indicated conditions and the dyeing is then rinsedwith water, an orange dyeing which has a very good fastness to washingand sublimation is obtained.

EXAMPLE 3

2 g of the dyestuff obtained according to Example 1 are finely suspendedin 2,000 g of water which contains 4 g of oleylpolyglycol ether, in apressure-dyeing machine. The pH value of the dye bath is adjusted to 4to 5 with acetic acid.

100 g of a fabric made of polyethylene glycol terephthalate are nowintroduced at 50°, the bath is heated to 140° in the course of 30minutes and dyeing is carried out for 50 minutes at this temperature.The dyeing is then rinsed with water, soaped and dried. When theseconditions are maintained, an orange dyeing which is fast to washing,perspiration, light and sublimation is obtained.

The dyestuffs described in the other examples give dyeings of equalquality by this process.

If, in the above example, the 100 g of polyethylene glycol terephthalateyarn are replaced by 100 g of cellulose triacetate yarn, dyeing iscarried out under the indicated conditions and the dyeing is then rinsedwith water, an orange dyeing which has a very good fastness to light andsublimation is obtained.

EXAMPLE 4

Polyethylene glycol terephthalate fabric is impregnated, on a padder, at40° with a liquor of the following composition: 20 g of the dyestuffobtained according to Example 1, finely dispersed in 7.5 g of sodiumalginate, 20 g of triethanolamine, 20 g of octylphenolpolyglycol etherand 900 g of water.

The fabric, which is squeezed off to about 100%, is dried at 100° andthen set for 30 seconds at a temperature of 210°. The dyed goods arerinsed with water, soaped and dried. Under these conditions an orangedyeing which is fast to washing, rubbing, light and sublimation isobtained.

The dyestuffs described in the other examples give dyeings of equalquality by this process.

What is claimed is:
 1. A dyestuff of the formula ##STR85## wherein R₁ isC₁ -C₅ alkyl, phenyl, tolyl, methoxyphenyl, ethoxyphenyl, chlorophenyl,nitrophenyl, 4-pyridyl or carboxyl -C₁ -C₃ -alkylphenyl;X is --COOH,--COO.sup.⊖ cation.sup.⊕, --COOR₁ ¹, --COQ or --CN; Q is --NHR₂ ¹ or--NR₂ ¹ R₃ ¹ ; R₁ ¹, R₂ ¹ and R₃ ¹ independently represent C₁ -C₁₈ alkylwhich is unsubstituted or monosubstituted by C₁ -C₄ alkoxy, hydroxy,chloro, bromo, cyano, carboxyl, carb-C₁ -C₄ -alkoxy, sulfo, carboxamidoor acetoxy; cyclopentyl; methylcyclohexyl; trimethylcyclohexyl;cyclohexyl; or phenyl, benzyl or phenthyl which are unsubstituted ormonosubstituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy or halo; R is hydrogen;alkyl of 1-8 carbon atoms, hydroxyalkyl of 2-3 carbon atoms; alkoxyalkylof 3-8 carbon atoms; β-chloroethyl; 62 -cyanoethyl; alkoxycarbonylethylwhere the alkoxy group thereof has 1-4 carbon atoms; carbamoylethyl;N-monoalkyl or N,N-dialkyl carbamoylethyl where alkyl has 1-4 carbonatoms; cyclohexyl; benzyl; phenethyl; phenyl or allyl; The ring A and Bare unsubstituted or monosubstituted by (a) C₁ -C₄ -alkyl; (b) C₁ -C₄-alkoxy; (c) halo; (d) C₁ -C₄ -alkylmercapto; (e) C₁ -C₄ -alkylsulfonyl;(f) phenylsulfonyl; (g) benzylsulfonyl; (h) C₁ -C₄ -alkylcarbonylamino;(i) C₁ -C₄ -alkylsulfonylamino; (j) N-alkyl or (k) N,N-dialkylsulfonamido wherein alkyl has 1-4 carbon atoms; (1) nitro; (m) cyano;(n) --COOH; (o) --COCl; (p) --COQ or (q) --COOR¹ ₁ ; with the provisothat when ring A is substituted by (a) C₁ -C₄ -alkyl; (b) C₁ -C₄-alkylmercapto; (e) C₁ -C₄ -alkyl-sulfonyl; (f) phenylsulfonyl; (g)benzylsulfonyl; (h) C₁ -C₄ -alkylcarbonylamino; (i) C₁ -C₄-alkylsulfonylamino or (j) N-alkyl or (k) N,N-dialkylsulfonamido wherealkyl has 1-4 carbon atoms, ring B is unsubstituted; and when ring B issubstituted by (m) cyano; (n) --COOH; (o) --COCl; (p) --COQ or (q)--COOR₁ ¹, ring A is unsubstituted or substituted by (b) C₁ -C₄ -alkoxy,(c) halo or (1) nitro M is hydrogen or a cation; and said cation is analkali metal, ammonium, pyridinium, C₁ C₄ -alkylammonium or a C₁ -C₄dialkylammonium cation.
 2. A dyestuff according to claim 1 of theformula ##STR86## wherein Y₁ is hydrogen, chloro, bromo, C₁ -C₄ alkoxy,nitro; and Y is --CN, --COCl, --COQ or --COOR₁ ¹.
 3. A dyestuffaccording to claim 2, wherein Y is --COOR₁ ^(') or COQ.
 4. A dyestuffaccording to claim 2, wherein x is CN.
 5. A dyestuff according to claim3, wherein Y is --COOR₁ ^(') and R₁ is C₁ -C₁₈ alkyl.
 6. A dyestuffaccording to claim 2, wherein Y is --COQ.
 7. A dyestuff according toclaim 1 of the formula ##STR87##
 8. A dyestuff according to claim 1 ofthe formula ##STR88##
 9. A dyestuff according to claim 1 of the formula##STR89##